Certain oxyalkylation derivatives of polyepoxide modified phenol-aldehyde resins



Patented Dee. 1,6, 1955 2 864 806 of said aforementioned copending application,- Serial Number 324,814, filed December 8, 1952, except that the CERTAIN OXYALKYLATION DERIVATIVES F polyepoxides employed are characterized byv being essen! POLYEPOXIDE MGDIFRED PHENOL-ALDEHYDE tially hydrophile in character instead of hydrophobe-in' RESINS 5 character. As noted in the aforementioned copending lication Serial Number 324 814 filed Decemberv 8 l nDe Groote St. Louis and Kwan-Tm Shen Brentapp 4 ,l I L arb ed, Mm, asdignors to Petrolite (lorp oratioii, Wil- 1952 h POIYFPOXIdFS invariably contam two or more mingmn, Del a corporation of Delaware phenolic nuclei but in any event have at least 6 and usually more carbon atoms in uninterrupted group or NO D ()ligim] app El j 1 s 5 10 chain and thus contribute essential hydrophobe properties. Serial Divided and this apphcamm P Indeed, the invention of our copending application, Serial 301956seral Number 324,814 may be characterized by the use of 10 Claims (CL 9 53 diglycidyl compounds described in said copending application and also elsewhere. As for example, in U. S.

This application is a division of our co-pending appli- 2,500,449, dated March 14, 19,50, to Bradley, in which cation Serial No. 337,884, new Patent No. 2,792,352, there are described glycidyl ethers represented by the filed February 19, 1953. formula Our invention is concerned with new chemical products wherein R represents the divalent hydrocarbon radical or compounds useful as demulsifying agents in processes of a dihydric phenol and n is an integer'of the series or procedures particularly adapted for preventing, break- 0, 1, 2, 3, etc. More specifically, such diglycidyl gathers ing or resolving emulsions of,the water-in-oil type and may be illustrated by the following formula 0 CH3 CH 0 C HDCHOHz O+ OCH2CHOHOH2 OC J-OCHz( H }H: i- CH: In (IE3 V particularly petroleum emulsions. Our invention is also wherein n is an integer of the series 0, 1, 2, 3, etc. concerned with the application of such chemical products In contradistinction to such diglycidyl'ethers which inor compounds in various other arts and industries as well troduce an essentially hydrophobe radical or radicals, the as with methods of manufacturing the new chemical prodpresent invention is characterized by analogous comucts or compounds which are of outstanding value indepounds derived from diglycidyl ethers which do not intromulsification. duce any hydropho-be properties in its usual-meaning Attention is directed to our copending application but in fact are more apt to introduce hydrophile prg'zdaerg Serial Number 324,814, now abandoned, filed Decemties. Thus, the 'diepoxides employed in the present invenber 8, 1952. Said copending application relates to a 40 tion are characterized by th e fact that the divalent radical process for breaking petroleum emulsions of the water-inconnecting the terminal epoxide radicals contains. less oil type characterized by subjecting the emulsions to the than 5 carbon atoms in an interrupted, chain. Po -finaction of a demulsifier including synthetic hydrophile stance, a simple member and one of the most readily, products; said synthetic hydrophile products being oxyavailable members of the class of diepoxides described in alkylation derivatives of the reaction products of certain our aforementioned copending application, Serial phenol aldehyde resins, therein described in detail, with ber 324,814, filed December 8, 1952, is certain phenolic polyepoxides, also therein described in I on t we detail. Of particular importance in the process of said H H s H H a H I co-pending application are the o-xyalkylation derivatives O -g' Ogo\.7ont

of the reaction products of phenol-aldehyde resins de- 5 I rived from difunctional mo-nohydric phenols and alder It is to be noted in this formula the terminal epoxy hydes having not over 8 carbon atoms, particularly, formradicals are Separated by the divalent hydrophobe gmup aldehyde, in which the difunctlonal monohydric phenol OH I residue is derived from a hydrocarbon substituted phenol, H I H with phenolic diepoxides of the following formula: C (IDOOE 9 C 3 C The diepoxides employed in-the present invention are a 0 2 obtained from glycols such as ethylene glycol, diethylene and cogenerically associated compounds formed in their gly l, PI PY g y p pylen E l/C rip opylene.

preparation. y b y e e ly ol dibuty sa g y o wtr lqu ylane.-

" Th P e t in n e s ab s to he n en on yc l; l cerol. dig yqqrol, triglycerol, and similar 3 pounds. Such products are well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be nonaryl or aliphatic in character. The diglycidyl ethers of copending application, Serial Number 324,8l4, filed December 8, 1952, are invariably and inevitably aryl in character.

The diepoxides employed in the present invention are usually obtained by reacting a glycol or equivalent compound such as glycerol or digylcerol with epichlorohydrin and subsequently with an alkali. Such diepoxides have been described in the literature and particularly the patent literature. See for example, Italian Patent 400,973, dated August 8, 1941. See also British Patent 518,057, dated December 10, 1938. See U. S. Patent 2,070,990, dated February l6, 1937, to Groll et al. Reference is also made to U. S. Patent 2,58l,464, dated January 8, 1952, to Zech. This particular last mentioned patent describes a composition of the following general formula in which x is at least 1, z varies from less than 1 to more than 1, and x and z together are at least 2 and not more than 6, and R is the residue of the polyhydric alcohol remaining after replacement of at least 2 of the hydroxyl groups thereof with the epoxide ether groups of the above.

Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it sometimes is desirable to dilute the compound containing the epoxy rings before reacting with an amine condensate. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene,

dioxane, possibly various ketones, chlorinated solvents,

dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated. otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred, to as polyepoxides. They usually represent, of course, 1,2- epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from thestandpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane (l,2,3,4 diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric compounds containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. Note, for example, that said U. S. Patent No. 2,494,295 describesproducts wherein the epoxide derivative can combine with a sulfonamide resin. The intention in said U. S, Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristics of a comparatively insoluble resin. Sim ply for purpose of illustration to show a typical diglycidyl ether of the kind herein employed, reference is made to the following formula:

or if derived from cyclic diglycerol the structure would be thus:

Commercially available compounds seem to be largely the former with comparatively small amounts, in fact comparatively minor amounts, of the latter,

Having obtained a reactant having generally 2 epoxy rings as depicted in the next to last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any phenol-aldehyde resin by virtue of the fact that there are always present reactive hydroxyl radicals which are part of the phenolic nuclei.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and a phenolaldehyde resin. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the phenol-aldehyde resin to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

in which n is a small whole number less than 10, and

usually less than 4, and including 0, and R represents a divalent radical as previously described being free from any radical having more than 4 uninterrupted carbon issimply an abbreviation for the resin which is described in greater detail subsequently.

vIn recapitulation then the present invention relates to synthetic hydrophile products; said products being oxyalkylation derivatives of the reaction products of certain phenol-aldehyde resins, hereinafter described in detail, with certain non-aryl hydrophile polyepoxides, also hereinafter described in detail. Of particular importance are the oxyalkylation derivatives of the reaction products of phenol-aldehyde resins derived from difunctional monohydric phenols and aldehydes not having over 8 carbon atoms, particularly, formaldehyde, in which the difunctional monohydric phenol residue is derived from a hydrocarbon substituted phenol, with non-aryl hydrophile polyepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom if subsequently replaced by the radical H H H o o /oH in the epoxide, is water soluble.

This invention is also concerned with the intermediates, i. e., the products obtained by reaction involving the non-aryl hydrophile diepoxides and the phenol-aldehyde resins. Such intermediates have utility for purposes other than oxyalkylation as, for example, by reaction with alkylene imines such as ethylene imine or propylene imine. Such intermediates can be converted into valuable cation-active materials.

As far as the use of the herein described products goes for the purpose of resolving petroleum emulsions of the water-in-oil type, and also for that matter for numerous other purposes where surface-active materials are effective, and particularly for those uses specified elsewhere herein, we prefer to employ oxyalkylated derivatives, which are obtained by the use of mono-epoxides, in such manner that the derivatives so obtained have suflicient hydrophile character to meet at least the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various oxyalkylated derivatives obtained particularly by use of ethylene oxde, propylene oxide, etc., may not necessarily be xylenesoluble although they are xylene-soluble in a large number of instances. If such compounds are not Xylenesoluble the obvious chemical equivalent, or equivalent chemical test, can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mlxture to dissolve the appropriate product being exam'ned and then mix with the equal weight of xylene, followed by addition of water. Such test obviously is the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Another peculiarity of the compounds herein described is that they may pass into a comparatively high molecular weight range and be effective for various purposes, not only for the resolution of petroleum emulsions but also for other industrial uses described in detail elsewhere. This characteristic may be related to the fact that the initial resin molecule, obtained in turn from two resin molecules combined by means of a polyepoxide as described, results in a fairly large molecule. We have found we can obtain compounds effective for purposes where surface-active materials are employed, whether it be the resolution of petroleum emulsions or other uses, in which one part of the derivative obtained by the polyepoxide reaction is combined with 50 parts, by weight, of the a kylene oxi he in m p l epq e a ve m y n ri ute s m at lessthan 2% of t e total oxyalkylated molecule. The word oxyalkylated is employed in this sense for purpose of convenience in referring to the mono-epoxide derivatives only.

For purpose of convenience what is said hereinafter will be divided into six parts:

Part 1 is concerned with the non-aryl diepoxides can ployed with reactants;

Part 2 is concerned with suitable phenol-aldehyde resins to be employed in reaction with the diepoxides;

Part 3 is concerned with reactions involving the two, preceding types of materials and examples obtained by such reaction. more than a reaction between two moles of a previously prepared phenol-aldehyde resin as described and one mole of a specified diglycidyl ether so as to yield a new, and larger resin molecule;

Part 4 is concerned with the oxyalkylation of the pre-, viously described resultant or cogeneric mixture whicn, for sake of simplicity, may be referred to as a diepox idc derived dimer. Such language is merely an approximation of its structure. Oxyalkylation is more conveniently employed in the text to indicate the use of the previously indicated monoepoxides;

Part 5 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 6 is concerned with uses for the products herein described, either as such or after modification, including uses in applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 Reference is made to previous patents as illustrated in the manufacture of the non-aryl diepoxides' employed as reactants in the instant invention. Morespecifically, those patents are the following: Italian Patent 400,973, dated August 4, 1941; British Patent 518,057, dated December 10, 1938; U. S. Patent 2,070,990, dated February 16, 1937, to Groll et al.; and U. S. Patent 2,581,464, dated January 8, 1952, to Zech. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by theuse of peroxides or by other suitable means and the diglycidyl others may be indicated thus 7 In some instances the compounds are essentially derivatives of etherized epichlorohydrin or methyl epichlorohydrin. Needless to say, such compounds can be derived from glycerol monochlorohydrin by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent 400,973.

CHzCHCHzOCHzCHCHz Another type of diepoxide is diisobutenyl dioxide as described in aforementioned U. S. Patent 2,070,990, dated The diepoxides previously described may be indicated the following formula Generally speaking, this involves nothing.

7 in'which R represents a hydrogen atom or methyl radical andfR'" represents the divalent radical uniting the two terminal epoxide groups, and n is the numeral or .1. Asprevioiisly pointed out in the case of the butadiene derivative, 11' is 0. In the case of diisobutenyl dioxide R is CH -CH, and n' is 1. In another example previotisly referred to R" is CH OCH, and n is 1.

However, .for. practical purposes the only diepoxide available in quantities other than laboratory quantities is a derivativetof glycerol or epichlorohydrin. This partic-' ular diepoxide is obtained from acyclic diglycerol and epichlorohydrin or equivalent thereof in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been previously suggested, instead of starting with glycerol or a'glyc'erol derivative, one could start with any one of a number of glycols .or polyglycols and it is more convenient to include. as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin.

presented the formula becomes In the above formula R is selected from groups such as the, following:

' It isto be noted that in the above epoxides there is a complete absence of (a) aryl radicals and, (b) radicals in which 5 or more carbon atoms are united in a single uninterrupted single group. R is inherently hydrophile in character as indicated by the fact that it is specified that the precursory diol or 'polyol HCROH must be water soluble in substantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that a polyepoxide such as H H H H H harass substituent hydrocarbon radical.

in which R, is c,H, oH) it isobvious that reaction as:

another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R;

, happened to be C3H (OH)OC H (OH), one could obtain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninter-f' rupted chain. This particular diglycidyl ether is ob-' tained by the use of epichlorohydrin in such a manner that approximately four moles of epichlorohydrin yield one mole of the diglycidyl ether or, stated another way, it can be considered as being formed from one mole; of acyclic diglycerol and 'two moles of epichlorohydrin so as to give the appropriate diepoxide. The molecular weight is approximately 370 and the number of epoxide groups per molecule are approximately two. For this reason, in the first of a series of subsequent examples this particular diglycidyl ether is used, although obviously any of the other previously described would be just as suitable. For convenience, this diepoxide will; be referred to as diglycidyl ether A, illustrated by a prior formula. Using laboratory procedure we have reacted diethylene. glycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound ferring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in grams instead of pounds.

Probably the simplest terminology for these polyepoxides, and particularly diepoxides, to differentiate from comparable aryl compounds is the terminology epoxyalkanes and, more particularly, polyepoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The principal class properly may be referred to as polyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction ofcombining erythritol with a carbonyl compound, such as formaldehyde or acetone, so as to form the 5-memberedring, following by conversion of the terminal hydroxyl' groups into epoxy radicals.

PART 2 This part is concerned with the preparation of phenol: aldehyde resins of the kind described in detail in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications: said aforementioned patent is limited to resins obtained from di j functional phenols having 4 to 12 carbon atoms in the For the present purpose the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecylphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexa decylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made-alsoto the following U. S. Patents-Numbers" 9 2,499,365, 2,499,366, and 2,499,367, all dated March 7, 1950, to De Groote and Kaiser. These patents, along with the other two previously mentioned patents, describe phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C carbon atom also being very satisfactory. The increased cost of the C and C carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins useful as intermediates for preparing the products of the present application, and reference is made to that patent for such detailed description and to Examples 10 through 103a of that patent for examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol, reference in each instance being to the difunctional phenol, such as the orthoor para-substituted phenol or a mixture of the same. Such resins are described also in issued patents, for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

It is sometimes desirable to present the resins herein employed in an over-simplified form which has appeared from time to time in the literature, and particularly in the patent literature; for instance, it has been stated that the composition is approximated in an idealized form by the formula H OH R R R In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenolic nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

In the above formula the aldehyde employed in the resin manufacture is formaldehyde. Actually some other aldehyde such as acetaldehyde, propionaldehyde, or butyraldehyde may be used. The resin unit can be exemplified thus:

OH OH Rllll R" l.

employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purpose of convenience suitable resins are characterized in the following table:

Table I M'ol. wt. of resin molecule (based on n+2) Example Position number of R Tertiary amyl Nonyl Tertiary butyl Tertiary amyl Nonyl Tertiary but Tertiary amyl l onyl .t Tertiary butyl H 3250 on owo Tertiary amyl N w w r en -m m t t rm-r CDOIGiCnHOvBQ ouboqoo 00 W9??? PPN Hexyl Oyclohexyl PART 3 As previously stated, the intermediate reactions involve two moles of a phenol-aldehyde resin of the kind previously described, and one mole of a diglycidyl ether as described. The reaction is essentially an oxyalkylation but, for sake of convenience is differentiated from the subsequent oxyalkylation procedure which involves a monoe poxide only. Since the polyepoxide is non-volatile as compared, for example, to ethylene oxide, the reaction is comparatively simple. On the other hand, purel'y as a matter of convenience, one generally would con- 12 which; of course, is suitable in the oxyalkylation step involving the monoepoxides described subsequently. The solvent selected may depend on the ability to remove it by subsequent distillation if required.

duct both classes of reactions in the same equipment. In Example 117 other words 'the two moles of phenol-aldehyde resin would be re acted with a polyepoxide and then subse- F Th6 Phehohformaldehyde Tesht p y was the P que fly ith a id I any event, h l previously'identified as 38a, havlng a molecular weight epoxide reaction can be conducted in an ordinary rei pp l' the amount p y was 1408 action vessel, such as the usual glass laboratory equipgrams- Th6 reslh was Y Powdered and 1,000 grants ment. Thls 1s partlcu larlytrue of the kind used for resin 05 Xylene h was heateft to pp manufacture as described in a number of patents, as for i y f surged tl l solutlonthwas fi zi example previously mentioned U. S. Patent No. 2,499,365. pfi grams 0 $0 "1111 the 3 ate all One can use a variety of catalysts in connection i h r and stirring continued until complete solution or dlSflh a h s? of sameil titi Jes a???2 32302322; epoxl e. 11 act, t e reactlon wi go at an extremey e a 15 e P slow rate without any catalysta t all. The usual catalysts dlepoxlde. prevlously Identified as p0lyep0X1de A, e includealkaline materials such as caustic soda, caustic ggged- It Wigs ailded 1n lsglutloln form and mixed8 potash, sodium methylate, etc. Other catalysts may be grams 0 $0 Veht- Vent use was a acidic in nature and are of the kind characterized by mature Xylene and dlethyiether of ethyleneglywl- Iron and tin chlorides. Furthermore, insoluble catalysts h sohltlohlwfls adfted dropwlse- Just before t s'uch as clays or specially prepared mineral catalysts have 1 011 :f thg dlqifgldecthe temlple-atue wi l; ra sed to been used. For practical purposes it is best to use a Somew at a We w-heaf 6 time catalyst which can remain in the reaction mass and will quifcd 9 add the po fi ppf y 2 h continue to serve as a catalyst in connection with the i igtgg ig fl gl d g l l p fi d pp oxyalkylation employing the monoepoxide. For this Y e P uct wast 611 a owe to T6 at reason we have preferred to use a small amount of finely h PP 'Q t temperature for the next 21/2 hoursgigided caustic soda;l or sodlurraidmetllagiatg /as a cgtglyst g i S 581F104 l 2'3 s 3( c N 3 23::

e amount enera em 0 is or o e empera the [086 Y 0 a 011 8 th lk li l p y a o was then allowed to proceed for about 8 hours longer Actually, the reactions of polyepoxides with various and pa f the Xylene was y megns ti -eaat' tra sotattteen te resln rnaterlals have been thoroughly descrlbed 1n the V511. a Ph Pm t l d Pen t a roximatel 140 l terature and the procedure 1s, for all purposes, the same P e p a 0 PP y as W1t(h1 glYCld whlcl ISPdCSCZIbBd 1n detail 1n the next C. lltefll lxlngtwas thenlcontlnltliedtfltlfither dWltFtgie rss'uccee lng part, to wit, art mova o a 1 more xy ene an a e en 0 1s a d The :se of an excessive t1amount oi czlttalyd st inlay prgt l sh llg o 'g fint p i l t t e zi d PP i uce si e reactions as in e case 0 gyci e. or t e ma 6 e Overa Feat! 1011 P 0 was sake of simplicity the procedure will be illustrated by r At the g 5 thlis tinge thesre a a g residue examplesbut particular reference is made again to the eqlllv t to P a Y 655 t an t e Ottom 0 fuiither disiussion of oxyalkylation reactions and prothe l a g flask p t l gs Shght h c l t ig ce ures in art 4. was a e approxlma ey grams, 1n or er 0 ave It goes without ayin that th rea ti n fake place the final reaction mass represent about one-half reaction in an inert solvent, i. e., one that is not oxyalkylationmass and one-half solven Subsequent tests in an tWapo' susceptible. Generally speaking, this is most convenientrating dish, with due altowahce for the g y s 1y an aromatlc solvent such as xylene or a hlgher bolllng Showed theft was approximately Solvent and 51 A2 colal tar sbolventl, gar else a similar high boiling arlomatic realcttllon mas: I d f 1 1 ht so vent o taine rom petro cum. ne can emp oy an e PIOCB 11 31 i 9 Course, 15 l? 6 8 oxygenated solvent such as the diethylether of ethylene of h h P5611 Said P P Y 3180 In hght 0f glycol, or the dlethylether of propylene gly ol, or i l what 1s sald 1n the next sectlon. Varlous examples obethers, elther alone or in combination with a hydrotamed 1n substantlally the same manner are enumerated carbon solvent. The solvent so selected should be one and described in the following tables:

Table I] Dissolved in 30-20 1 mixture Percent- Resin Dissolved Sod. Polyep- Polyepxylene l e-action Approx. age sol- Ex.No. Resin used used, in xylene, methylate oxide oxide and ditemp. range, time of vent ill grams grams used, used used, ethyl 0. reaction, final grams grams other of hrs. product ethylene glycol, l grams 1, 40s 1, 000 20 A 370 500 00-100 l7 l0 1, 985 1, 000 35 A 370 500 00-155 15 50 1, 705 1, 000 40 A 370 500 20155 18 51 2,050 1, 000 28 a 370 500 85-160 22 50 2,380 1,000 38 A 370 500 05-100 19 40 2,535 1,000 27 A 370 500 85.155 22 51 1,890 1,000 23 A 370 500 100-145 18 50 000 1, 000 25 A 370 500 85-160 17 40 2,913 1, 000 30 A 370 500 -145 20 51 2, 017 1, 000 as A 370 500 00-100 10 50 1, 272 1, 000 23 A 370 500 -160 20 50 1, 40s 1, 000 32 A 370 500 -145 18 51 1, 480 1, 000 27 A 370 500 80-145 17 40 1, 210 1, 000 25 A 370 500 85155 20 50 1, 300 1,000 2s A 370 500 80-150 18 I 40 1.110 1.000 23 A 370 500 00-155 17 51 1,380 1, 000 2s A 370- 500 85-100 22 t 50 1, 590 1,000 20 A 370 500 00-100 18 s0 Table 111 stantially conventional for the oxyalkylation of compounds having labile hydrogen atoms, and for that reason a, de- Pmbab 1e tailed description of the procedure is omitted and the Resin COH- f f 11515.01 Amt.of number or process will simply be illustrated by the followlng ex- Ex.No.- denstate g g h product, solvent, hydroxiyls amples. use grs. rs. e1 1110 eroduct g p cule Example 1d 1 763 3 578 15 The oxyalkylation-susceptible compound employed is 2:343 4:665 33 g the one previously designated as 1412. The preparation 3,152 i, r 00 13 of 14b is described in Tables II and III. 2:735 5:457 1 15.65 pounds of diepoxide-derived compound or mix- 2.890 5.765 2,875 13 ture designated as 14b was dissolved in approximately 2, 246 4, 477 2, 231 13 3,015 6,015 3,000 13 an equal we1ght of xylene as a solvent. The amount 3. actually used was 15.5 pounds. To this there was added 11627 5: 1:612 10 1.56 pounds of finely pulverized caustic soda. The mixggg lg 9 ture of solvent, diepoxide-derived product and catalyst 1 31115 550 g was stirred so as to obtain a uniform mixture. The autofig; gag g clave employed had a capacity of approximately 25 gal- 1:735 51 1 5 9 lons. In other preparations small autoclaves, for in- 1.945 3,875 1,930 9 20 stance, 5, 10 or 15 gallons, have been used and in some instances autoclaves having a capacity of 35 to 50 gallons Table IV Dissolved in 50-50 mixture Percent- Resin Dissolved Sod. Polyep- Polyepxylene Reaction Approx. age sol- Ex.No. Resin used used, in xylene, methylate oxide oxide and ditemp. range, time of vent in grams grams used, used used, ethyl C. reaction, final grams grams ether of hrs. product ethylene glycol, grams 1, 408 1, 000 27 B 230 250 90-155 18 50 1, 985 1, 000 32 B 280 250 90-160 16 4o 1, 755 1, 000 35 B 230 250 85-155 17 51 2, 050 1, 000 26 B 230 250 90-160 20 49 2, 380 1, 000 28 B 230 250 85-160 19 50 2, 535 1, 000 38 B 230 250 80-145 22 51 1, 890 1, 000 27 B 250 250 100-145 18 40 2, 660 1, 000 23 B 230 250 85-155 17 50 2, 913 1, 000 25 B 230 250 90-155 19 51 2, 017 1, 000 26 B 230 250 85-160 22 49 1, 272 1, 000 38 B 230 250 90-160 18 50 1, 496 1, 000 26 B 230 250 80-145 20 51 1, 480 1, 000 27 B 230 250 100-145 17 49 1, 210 1, 000 28 B 230 250 85-155 19 50 1, 300 1, 000 25 B 230 250 80-150 20 51 1, 110 1,000 28 B 230 250 80-155 18 1, 380 1, 000 28 B 230 250 85-160 17 50 1, 590 1, 000 25 B 230 250 90-155 19 51 Table V have been used. In some instances, as a matter of convenience, the transfer of the reaction mass was made Probable nljgpligalgf Amt of Am. of number of from one autoclave to the other. Ex.N0. Resin reP'cfion product, solvent, hydroxyls In th1s partlcular run ad ustment was made in the product fig autoclave so as to operate at a temperature of approximately 125-130 C. and at a pressure of 10 to 15 1 613 g 3 178 1 565 8 pounds per square inch. The time regulator was set so 21193 4:265 21072 11 as to inject the ethylene oxide within approximately a 5 3g; 2 $22 half hour. The rotating stirrers were set so as to operate 2: 586 5: 057 2; 471 11 at approximately 400 R. P. M. The reaction went readily 2 332 2 3?? i 85? and, as a matter of fact, was completed in less than -a 2: 865 51 615 2: 750 11 half hour. Stirring was continued for about 40 minutes longer. The speed of reaction, particularly at the low 1,477 2,839 1,862 8 pressure, undoubtedly was due in a large measure to exigg 2 3g; ggg g cellent agitation and also to the high concentration of 1, 415 2,715 1,300 7 the catalyst. The amount of ethylene oxide introduced 333 Z was approximately equal to the initial weight of the 1,585 3,055 1,470 7 diepoxide-derived compound, i. e., 17.6 pounds. This 1'795 3'475 7 represented a molal ratio of about 40 pounds of ethyleneoxide per mole of diepoxide derivative. The theoretical PART 4 molecular weight at the end of the reaction was approximately 3,500. A comparatively small sample, less than In preparing oxyalkylated derivatives of products f 50 g ams was withdrawn merely for exa1n1nat1on as far the kind which appear as examples in Part 3, we have as solubility or emuls1fy1ng power was concerned and found it particularly advantageous to use laboratory also f PurpoSe of makmg, some tests In Vanous 011 fi f equipment which permits continuous oxypropylation and The {1111mm wlthfllrawn 80 Small that f oxyethylatiom The oxyethylation step is, f wurse, the cognizance of th1s fact was included in the data or in same as the oxypropylation step insofar that two low- Subsequent data presented In Tables VII, VIII, and boiling liquids are handled in each instance. The oxy- IX. In innumerable compa atlv oxyalkylations We have alkylation step is carried out in a manner which is subwithdrawn a substantial portion at the end of each step oxyalkylation with a different oxide.

Example 2d This simply illustrated the further oxyalkylation of Example 1d preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, 1d present at the beginning of this step, was obviously the same as at the end of the prior stage (Example 1b), to wit, 15.65 pounds. The amount of oxide present in the initial step was 17.6 pounds. The amount of catalyst remained the same, that is, 1.56 pounds, and the amount of solvent remained the same. The amount of oxide added was another 17.6 pounds, all additions of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyalkylation stepthe oxide added was a total of 35.2 pounds and the i'nolal ratio of ethylene oxide to diepoxide resin derivative was approximately 80 to 1. The theoretical molecular weight was 5,085. Conditions as far as temperature and pressure were concerned were the same as in the preceding period and in fact remained so during the entire series. For this reason, no further comment will be made in regard to either temperature or pressure. This applied also to the time period in this instance.

Example 3d The oxyalkylation preceded in the same manner as described in 1d and 2d. There was no added solvent and no added catalyst. The oxide added was 17.6 pounds and the total oxide at the end of the reaction was 52.8 pounds. The molal ratio of oxide to diepoxide resin derivative was approximately 120 to 1. The reaction time was the same as previously. The theoretical molecular weight was 6,845.

Example 4d Example 5d ;T'he oxyalkylation was continued with the introduction of another 17.6 pounds of ethylene oxide. The molal ratio at the end of the reaction period was approximately 200 to 1 and the theoretical molecular weight about 10,365.. The reaction time was one and one-fourth hours.

Example 6d The same procedure was followed as in the preceding steps with the result that at the end of the reaction period the ratio of oxide to resin derivative was 240to 1, and the theoretical molecular weight was approximately 12,125. The time required to add the oxide was two hours.

Example 7d 2 The procedure was the same as before, the amount of oxide added was the same as before, and the time required was approximately two hours. The ratio of oxide toresin derivative was 280 to 1 and the theoretical molecular weight was approximately 13,885.

' Example 8d This was the final oxyalkylation in this particular series. Theamour t of oxide added was the same as before and 16 the total amount of oxide in at the end of the step was approximately 141 pounds. The molal ratio of oxide to resin derivative was 320 to l and the theoretical molecular weight was approximately 15,645. The time required was a little over two hours, to wit, two and one fourth hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, VI, VII, VIII, and IX.

In substantially every case a -gallon autoclave was employed, although in some instances the initial oxyethylation was started in a IS-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Table VI it will be noted that com pounds 1d through 40d were obtained by the use of ethylene oxide, whereas 41d through 80d were obtained by the use of propylene oxide alone.

Thus in reference to Table VI it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-sosceptible compound, to wit, the diepoxide treated resin, is indicated in the second column.

The amount of such derivative used is shown in the third column.

Assuming that ethylene oxide is employed, as happens to be the case in Example 1d through 40d, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the intial step since no oxide is present there is a blank. 7

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent xylene employed.

The 8th column states the amount of alkylene oxide derivative present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 8 coincides with the figure in column 3.

Column 9 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

oxide was employed.

Column 11 shows the catalyst at the end of the reaction period.

Column 12 shows the amount of solvent at the end 0 the reaction period. Column 13 shows the molal ratio of ethylene oxide derivative.

Column 14 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the.

Column 10 can be ignored insofar that no propylene to wit,

Moleoj. wt. ased orctlcal value Propl. b oxide on theto oxycmpd.

Molal ratio Ethl. oxide to oxyalkyl alkyl. suscvpt. su scept.

cmpd.

S01- vent, lbs.

000000005 5555550000 00000000 0000 000 555 .n 55555555777777773333 33.522222 2255mm555wmmmmwmmmFinnnhwmmmmmmmmmmw?wmmm 5555555888888889999999988888BR8555=micmiiiiii 9 11111112222229.211111111111111L1l11111111111MMMm%%%%%%%%wwwwwwwlmmmmwmmmmlll H111 lbs.

66666660000000005555 555333333338888888 66 6 06 5555555555555 5555555555 8888 55555555888888889999 999880088888- 777777m 55 5 80000008008899999%9988888888w mm m7777 Composition at end Propl. Cataoxide, lyst,

a and 79d. These compounds involve the use oxide, lbs.

0 0 0 6 8 7 om 0 0 0 L1 7429 4197 31964 2 58 0 24630 1356 023 233456 2 .l 111 s O-S* Ethl. cmpcl, lbs.

5555555555555555555555550000000 555555555555555555555555 333333336066066000066"O66o 90 999Dum 444444443333333366666666 5 8 2 that these compounds were designated by e numbers; that is, 1e, 2e, etc, through and including 322. They are derived in turn from compounds of d series, 35a, 39,

pounds 1d through 40a were obtained with the use of ethylene oxide, it is obvious those obtained from 35d and Table VI vent,

lbs.

Prop]. Cataoxide, lyst,

Composition before oxide, lbs.

, Examples 41 d through 0-s- Ethl.

lbs.

ex. No.

Referring now to Table VI 8011, which, in essence are the counterparts of Examples 1d through 40d except the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as previously explained three columns are blank, to wit, columns 4, 9, 5 of both ethylene oxide and propylene oxide. Since comand 13.

Reference is now made to Table VII. It is to be noted Ex. No.

0xyalkylation-susceptible.

19 39d'involve the use of ethylene oxide and propylene oxide afterwards. inversely, those compounds obtained from 75d and 79d obviously were obtained from a previously prepare compound where propylene oxide was used first.

is used along witheither one of the two oxides just mentioned, or a combination of both of them.

The resins which are employed as raw materials vary from fairly high melting resins to resins melting near the In the series of 6 compounds, 1e through and includ- 5 f g p lof wczitter,t tlo oltjhelr prgdtiliaclts glgietelglellxllag ing 322, it will be noted that it required a duplication of 33: g g g gg gi gs 31:10 water ghite u re r c m to wit 35 g g g 4 prepa ed 0 Pounds to products which are dark amber or reddish amber in aph 1 I pearance. In some instances they are tacky solids, or even It Is to be noted that leference.to t 8 Cam m Tab 10 liquids at ordinary room temperatures. After treatment VIII refers to the mtal catalyst the cam yst with diepoxides of the kind herein employed the resultant from the first step plus added catalyst 1f product is usually at least as dark, perhaps darker, than The same true In regard to the Solvent Refar' the initial resin. The solvent can be removed readily by fince to the Solvent refers to the P Solvent Present distillation, particularly vacuum distillation. The product i from the first oxyalkylatlon Step P added 15 obtained after treatment with the described diepoxide is Solvent 1f Y- apt to be somewhat softer and more liquid than the It Will be noted also that under the molal ratio the original material. In some instances a tackiness develops values of both oxides to the resin condensate are included. which is suggestive of cross-linking in some obscure The data given in regard to the operating conditions is manner. substantially the same as before and appears in Table IX, When products of the kind prev1ously described are h products resulting from these procedures may intended for subsequent react1on, such as oxyaikylation, contain modest amounts, or have small amounts, of the Solvent and Catalyst y be permuted to remain for solvents as indicated by the figures in the tables. If deultimate sired the solvent may be removed by distillation, and Oxyalkylatlon, particularly exhaustive oxyalkylatlon particularly vacuum distillation. Such distillation also tengs 3 do a g z of .thmgs i? as reduce the 3 may remove traces or small amounts of uncombined 3 5 g g g zi ggg fs i sg g gfz g oxide, if present and volatile under the conditions emp y y gg 1 f th d m 1 In any event whether the solvent is to be removed, or vfous use 0 6 g e an p py jg the product bleached at either stage, it is simply a matter oxide co'mbmatwn one nee rst use 01:16 6 of the intended ultimate use. If employed for the resoluand thenfhe other but one can h two Oxides and tion of petroleum emulsions there is no need to eliminate Q Qbialn What may be termcl an lndlfierent Oxyalkyla' any alkalinity and no need to eliminate color or solvent. tion, 1. e., no attempt to selectively add one and then the If the product i to b l d i h manufacture other, or y other val'lafltof varnish resins the procedure should be conducted so N ed ess to y, 0116 Could Start With ethylenfl Oxide as to hold the color at a minimum, or else the final prodand then use propylene oxide, and then go back to ethyluct or intermediate product can be further bleached in one oxide, or, inversely, start with propylene oxide, then the usual manner using earth, bleaching chars, or the like. use ethylene oxide, and then go back to propylene oxide, Ultimately the solvent could be removed in any suitable or, one could use a combination in which butylene oxide manner by distillation, including vacuum distillation.

Table VII Composition before Composition at end Molalratlo Molec. Ex. N0. wt-

O-S O-S Ethl. .Prnpl. Cnta- Sol- 0-8 Ethl. Propl. Cata- Sol- Ethl. Propl. based cmpd.. cmpd.. O OXille. 13 st, vent, cmpd., oxide, oxide, lyst, vent, oxide oxide on theex.l\'o. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. to oxyto oxyoretloel alkyl. allryl. value snsoept. suscept cmpd. cmpd.

'Oxyalkylation-susceptible.

Table III-Continued Max. Max. Solubility Ex. temp., pres., Time, N0. C. p. 5.1 hrs.

Water Xylene Kerosene -15 1% Soluble Insoluble. 10-15 2 Emulsiflable-. Do. 10-15 2 do Do. 10-15 2% Do. 10-15 2% D0. 10-15 3 Soluble 10-15 2% Insoluble. 10-15 54 Do. 10-15 51 D0. 10-15 1 Do. 10-15 1 Do. 10-15 1% Do. 10-15 2 Do. 10-15 2 Do. 10-15 6% Dlsperslble. 10-15 Insoluble. 10-15 1 D0. 10-15 1 Do. 10-15 1% d Do. 10-15 2 (I Do. 10-15 3 d do D0. 125-130 10-15 3% Soluble Insoluble Do.

time required to introduce the second alkyleneoxide employed.

PART 5 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both 00- and water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials of our invention when employed as demulsifying agents.

The materials of our invention, when employed as treating or demulsifying agents, are used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of con ventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of'heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Oxyalkylatcd derivative, for example, the product of Example 4e, t

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A-high-boiling aromatic petroleum solvent, 15%; lsopropyl alcohol, 5%. The above proportions are all weight percents.

PART 6 The intermediate resinous products described in Part 3, preceding, can be oxyalkylated and employed for various purposes and particularly for the resolution of petroleum emulsions of the water-in-oil type as described in detail in Part 5, immediately preceding.

Such resinous products, however, without being subjected to oxyalkylation can serve for other uses as described in U. S. Patent No. 2,610,955, dated September 16, 1952, to De Groote and Keiser. Furthermore, such resinous materials can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine, one may cmploy what is a somewhat equivalent material, to wit, a dialkylaminocpoxypropane of the structure wherein R and R" are alkyl groups.

It is not necessary to point out that after reaction with a reactant of the kind described which introduces a basic 7 in the laundering, scouring, dyeing, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have their utility as such but they can serve as initial materials for "I more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification,

ctherization, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricatingoils, both thosederivedfrom petroleum and synthetic lubricating oils. Also, they can be used as additives. to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

Comparable compounds which can serve the various purposes previously enumerated, in both the resinous stage and the oxyalkylated stage, are obtained from another class of resins, i. e., those in which the phenolic nuclei are separated by a radical having at least a 3- carbon atom chain and are obtained, not by the use of a single aldehyde but by the use of formaldehyde, in combination with a carbonyl compound selected from the class of aldehydes and ketones in which there is an alpha hydrogen atom available as in the case of acetaldehyde or acetone. Such resins almost invariably involve the use of a basic catalyst. Such bridge radicals between phenolic nuclei have either hydroxyl radicals or carbonyl radicals, or both, and are invariably oxyalkylation-susceptible and may also enter into more complicated reactants with basic secondary amines. The bridge radical in the initial resin has distinct hydrophile character. Such resins or compounds which can be converted readily into such resins are described in the following patents. Such analogous compounds are not included as part of the instant invention.

U. S. Patent- No. Dated Inventor 2,191,802 Feb. 27, 1940 Novotny et al. 2,44% 4 Fife et 2, 5 t8. Sehritr pe 2,553 Do.

2,54 D0. 2,570,389 DO.

in which R is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the 2,4,6 position; and (B) non-aryl hydrophile polyepoxides containing at least two 1,2-epoxy rings obtained by replacement of oxygen linked hydrogen atoms in a water soluble polyhydric alcohol by the radical said polyepoxides being free from reactive functional groups other than 1,2-epo-xy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal epoxide groups is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; with the further proviso that said reactive compounds (A) and (B) be members of the class conlow-melting solids; and with the" further proviso that the reaction product be a member of the class of acylationand oxyalkylation-susceptible' solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; with the final proviso that the ratio of reactants be '2 moles of resin to 1- mole of polyepoxide; followed by an oxyalkylation step by means of an alpha-beta alkylene monoepoxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. Synthetic hydrophile products; said synthetic hydrophile products being the oxyalkylation derivatives of the reaction products of (A) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenolaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; and (B) non-aryl hydrophile hydroxylated diepoxides containing at least one ether linkage and two terminal 1,2-epoxy rings obtained by replacement of two oxygen linked hydrogen atoms in a water soluble polyhydric ether alcohol by the radical said hydroxylated diepoxide being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal epoxide groups is free from any radical having more than 3 uninterrupted carbon atoms in a single chain; and total number of carbon atoms in said diepoxide being not over 20; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nonthermosetting solvent-soluble liquids and low-melting solids; and with the further proviso that the reaction product be a member of the class of acylationand oxyalkylationsusceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; with the final proviso that the ratio of reactants be 2 moles of resin to 1 mole of diepoxide; followed by an oxyalkylation step by means of an alphabeta alkylene mono-epoxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

3. The product of claim 2 wherein the aldehyde is formaldehyde.

4. The product of claim 2 wherein the aldehyde is formaldehyde and R is substituted in the paraposition.

5. The product of claim 2 wherein the aldehyde is formaldehyde and R is substituted in the paraposition and the initial resin contains not over 6 phenolic units.

6. The reaction products of (A) an o-xyalkylationsusceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in 27 the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the 2,4,6 position; and (B) non-aryl hydrophile polyepoxides containing at least two 1,2-epoxy rings obtained by replacement of oxygen linked hydrogen atoms in a water soluble polyhydric alcohol by the radical said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal epoxide groups is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nontherrnosetting solvent-soluble liquids and low-melting solids; and with the further proviso that the reaction product be a member of the class of acylationand oxyalkylation-susceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction and with the final proviso that the ratio of reactants be 2 moles of resin to 1 mole of polyepoxide.

7. The reaction products of (A) an oxyalkylationsusceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which 'R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; and (B) non-aryl hydrophile hydroxylated diepoxides containing at least one ether linkage and two terminal 1,2-epoxy rings obtained by replacement of two oxygen linked hydrogen atoms in a water soluble polyhydric ether alcohol by the radical said hydroxylated diepoxide being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal epoxide groups is free from any radical having more than 3 uninterrupted carbon atoms in a single chain; and total number of carbon atoms in said diepoxide being not over 20; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nonthermosetting solvent-soluble liquids and low-melting solids; and with the further proviso that the reaction product be a member of the class of acylationand oxyalkylation-susceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction and with the final proviso that the ratio of reactants be 2 moles of resin to 1 mole of diepoxide.

8. The reaction products of claim 7 wherein the aldehyde is formaldehyde.

9. The reaction products of claim 7 wherein the aldehyde is formaldehyde and R is substituted in the paraposition.

10. The reaction products of claim 7 wherein the aldehyde is formaldehyde and R is substituted in the paraposition and the initial resin contains not over 6 phenolic units.

De Groote et al Mar. 7, 1950 Greenlee Sept. 12, 1950 

1. SYNTHETIC HYDROPHILE PRODUCTS; SAID SYNTHETIC HYDROPHILE PRODUCTS BEING THE OXYALKYLATION DERIVATIVES OF THE REACTION PRODUCTS OF (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOLALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 